CN107848048A - The surface protection film of humble gel - Google Patents
The surface protection film of humble gel Download PDFInfo
- Publication number
- CN107848048A CN107848048A CN201680040884.0A CN201680040884A CN107848048A CN 107848048 A CN107848048 A CN 107848048A CN 201680040884 A CN201680040884 A CN 201680040884A CN 107848048 A CN107848048 A CN 107848048A
- Authority
- CN
- China
- Prior art keywords
- resin material
- film
- refined
- microgel
- polyethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 2
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- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 description 2
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
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- HGVPOWOAHALJHA-UHFFFAOYSA-N ethene;methyl prop-2-enoate Chemical compound C=C.COC(=O)C=C HGVPOWOAHALJHA-UHFFFAOYSA-N 0.000 description 1
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B13/00—Conditioning or physical treatment of the material to be shaped
- B29B13/02—Conditioning or physical treatment of the material to be shaped by heating
- B29B13/022—Melting the material to be shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/84—Venting or degassing ; Removing liquids, e.g. by evaporating components
- B29B7/845—Venting, degassing or removing evaporated components in devices with rotary stirrers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/69—Filters or screens for the moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/76—Venting, drying means; Degassing means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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Abstract
The method that finished polymer resin material is provided.This method includes molten resin material, and is placed under the shear stress that scope is 250kPa to 400kPa, forms refined resin material.Resin material extrudable, that solidifying refinement is crossed, and cut into the resin granular material of microgel reduction, it is then fusible and extrude, form the film for reducing microgel.
Description
The cross reference of related application
The U.S. Provisional Application No.62/171 submitted this application claims on June 5th, 2015,473 priority, its whole
Disclosure is herein by reference in introducing.
Invention field
This invention relates generally to polymeric film material, and relate more particularly to polymer surfaces diaphragm, and form this
The method of kind film, it reduces the size of the gel included and microgel, raised and quantity.
Background of invention
Surface protection film, also referred to as mask, lining or lining paper film, it is essentially available for providing physical barriers, to prevent substrate
Damage, pollute, scratch, scratch or other breaking-ups.Surface protection film also can with lining paper film used interchangeably, to prevent soft and embrittlement
Optical film layer-to-layer adhesion or adhesion and the light regime purpose that is used to show in industry.Can be used mask, manufacturing, transport or
This protection is provided during storage before for example using substrate.Guarantor of this film as surface can be used in numerous applications
Coating is protected, the surface particularly for protecting relative smooth, for example (,) acrylic resin, cyclic olefin polymer (COP), PMMA,
The metal and glazed ceramics of makrolon, glass, polishing or japanning.For television set, monitor, phone, tablet personal computer, and its
The optical substrate of his display for example requires that mask pad both protects surface, and is not damaging, and does not leave bonding on the surface
Removed in the case of agent residue or other pollutants or particle.
Many optical substrates because the degree of irregularity in mask contact surface topography in itself cause it is sensitive also to damage.To the greatest extent
Manage generally planar, but the contact surface of any mask has the certain of sunk area (hole) and raised zones (projection) form
Degree of irregularity.It is raised especially worrying, because they can be applied in substrate thereon in mask causes corresponding transcription.
Up to date, most of optical substrates can tolerate the defects of small in mask contact surface.However, now, exploitation
Baseplate material for high-resolution applications causes harsher quality requirements.Even 1 or 2 micron of projection can not may connect
The surface of these materials is damaged by ground.In addition, these substrates require high-resolution optical detection, this must use mask original place
Realize.This means mask must not only printing opacity, and it must show very high transparency and definition for naked eyes
Check.Having previously been thought that the material of " low haze " has the definition for being insufficient to allow for this inspection, although in some cases, can
By using improved online camera arrangement, by the surface protection film compared with haze, detect and characterize defect.
These harsher requirements, which result in, substantially to be excluded to use some polymeric materials as high-resolution optical
Substrate mask.Because the film formed by this material (for example, usually polyolefin, and polyethylene (PE)) tends to wrap
The small polymer aggregation for being typically called " gel " or " flake " is included, they can not remove and in some cases even can
To be caused by expressing technique.Gel may include the polymer twine not melted for example, not melt/undispersed polymer, or
By aoxidizing the cross linked chain formed.Exist in thin polymer film this gel-be even less than 100 microns those (herein
In be referred to as " microgel " and sometimes referred to as " micro- flake ")-can cause to heave at film surface, as shown in figs. 1 and 2.These drums
Rising can be by the area of their plane form with surface right-angle view and by being generally flat the convex of surface measurement from film
Play height hpTo measure,
So far, only some relatively expensive polymer, for example, polyester can be used for manufacture meet most rigors with
For the film for the optical substrate for protecting current fine definition.High expectations provide by more cost efficient polymer, such as PE and
Other polyolefin are formed, but provide the surface protection film of the performance characteristic suitable with the PET masks of adhesive coating.
Summary of the invention
The method that one aspect of the present invention provides finished polymer resin material.This method includes molten resin material,
And be placed under the shear stress that scope is 250kPa to 400kPa, form refined resin material.This method can enter one
Step includes the resin material of extrusion and solidifying refinement.In certain embodiments, the polymer resin material mainly by a kind of or
A variety of polyolefin compositions.In special embodiment, the polymer resin material is mainly made up of polyethylene.
Another aspect of the present invention provides the method to form polymer film.This method includes providing mainly to be made up of polyethylene
Polymer resin material, and mix the polymer resin material and one or more antioxidant, form resin material mixture.
This method further comprises melting the resin material mixture, and is placed on the shear stress that scope is 250kPa to 400kPa
Under, form refined resin material.The refined resin material is then extruded, forms polymer film.In some embodiment party
In case, this method further comprises before extruding refined resin material and forming the action of polymer film, extrudes and solidifies
Refined resin material, the then refined resin material of melting extrusion and solidification, and be placed on cutting less than 70kPa
Under shearing stress.
Another aspect of the present invention provides the resin material being substantially made up of polyethylene, and the resin material does not have substantially
There is the microgel that full-size is more than 100 microns.In a particular aspect, by melting precursor resin material, and by its
It is placed under the shear stress that scope is 250kPa to 400kPa, refines the resin material.
Another aspect of the present invention provides a kind of thermoplastic polymer film being substantially made up of polyethylene, and the film is substantially
It is more than 100 microns of microgel without full-size.In special embodiment, thermoplastic polymer film has at least one
Individual nominal flat surfaces, the surface, which does not have from the nominal flat surfaces substantially, extends outwardly beyond 1.0 microns convex
Rise.
Another aspect of the present invention provides a kind of multi-layer thermoplastic polymer film, and it includes determining the first exterior film surface
Peel ply, and the adhesive layer that defines second exterior film surface relative with the first exterior film surface.In peel ply and adhesive layer
At least one microgel for being substantially made up of polyethylene and being substantially more than 100 microns without full-size.In some realities
Apply in scheme, both peel ply and adhesive layer are substantially made up of polyethylene, and it is micro- to be substantially more than 100 without full-size
The microgel of rice.In in these embodiments some, the film do not have substantially from the first or second exterior film surface to
The outer projection for extending beyond 1.0 microns.
Brief description
Fig. 1 be illustrate microgel size influence and on surface topography position film schematic cross-section.
Fig. 2 is to be included with what is embedded in it at the polymer film surface of microgel, the raised photo of display surface.
Fig. 3 is the schematic diagram of workable extrusion film production line in the method according to the invention.
Fig. 4 is the block flow diagram of method according to embodiments of the present invention.
Fig. 5 is the signal for implementing the shearing force extrusion device according to workable for the method for some embodiments of the invention
Figure.
Fig. 6 is the block flow diagram of method according to embodiments of the present invention.
Fig. 7 is the description that the Polymer membrane samples of the enlarged photograph with a part of sample are drawn；With
Fig. 8 is the sectional drawing for the membrane material photo for carrying out microgel measurement.
Detailed description of the invention
Explanation is intended being related to finished polymer resin material and many by its production polymeric film material by providing below
Specific embodiment and details, transmit the comprehensive understanding of the various embodiments of the present invention.However, it is to be understood that the present invention does not have
It is restricted in these specific embodiments and details, they are only to enumerate.It is further to be understood that possess this area common skill
Personnel in view of known system and method, it will be understood that using the present invention in its in any one of many alternative embodiments
The purpose and advantage of plan.
It is of the invention to provide by typically showing the poly- of such as polyolefin etc for being formed and retaining gel inclusion tendency
The method that compound produces the surface protection film of humble gel.The inventive method is usually related to the technique in expression surface diaphragm
During or the part as preliminary step, fluoropolymer resin is placed under very shearing force during melting.
As discussing in more detail below, shearing force processing can be used, before making in base polymer resin material not
Melting or the gel to tangle and microgel are broken and melted, but cause the shape in extruded material in the case of in the absence of additional measures
Into cross-linked gel and the microgel that does not melt or tangle.In the method for the invention, one or more measures can be used, calculate and hand over
Join the formation of gel.Therefore, gained extrudate is without big gel (longest dimension be more than 100 microns of gel), and with basis
Resin is compared with the extrudate formed using standard expressing technique by same polymer, is had significantly less and less micro- solidifying
Glue.
" film " used herein refers to that thickness is less than 1000 microns of sheet material or film.Surface protection film typically thickness
50 microns are may be significantly lower than that less than 100 microns and thickness.In this film, any microgel more than 10-20 microns can make film
Substantially planar surface significantly deform.Being appreciated that will be flexible if intending reference for the term " substantially planar " for film surface
Film be applied on flat surface, by for flat nominal regular surfaces.
It is well-known to occur the difficulty that gel and microgel are shown in the polymer film produced using standard technique
's.In typically extrusion film production line 100, such as illustrate in figure 3, typically pellet form or pellet and from side
The polymer resin material 10 of the combination of the recovery fine hair of edge finishing is fed in conventional extruders 110, makes resin material 10
Melt and extruded by die head 120 in the form of mesh 20.For curtain coating net, the slot die of routine is used.For blowing
For system net, circular or oval die head can be used.(for example, without side grinding sand (NSM) technique) in some embodiments, can be
The mesh 20 of extrusion resin material is stretched on casting roller 140 by using vacuum tank 130.In other embodiments (for example,
Side frosted (OSM) technique), vacuum aided may not be sought, be cast the material.It is appreciated that although illustrate and describe herein
Vacuum tank 130, but any suitable equipment for applying negative pressure can be used.Casting roller is typically smooth, to assign gained
The smooth substantially planar surface of casting films 30.However, in some embodiments, one or two surface of casting films can carry
It is provided with the surface of texture or composition.Casting films 30 can undergo extra processing, and the surface relative with smooth surface is aided in assign
Specific texture or pattern.This may include for example to heat casting films 30, is then directed to smooth roll and rubber or other are textured
Roller (not shown) between.Also film 30 can be repaired and arrive preset width.Gained film is wrapped on spool 150 for storing and/or transporting
It is processed further before defeated or use.
Fig. 3 expressing technique that enumerates shows to form monofilm.It is appreciated that can be by providing multiple extruders, each
The simple layer described is formed in Fig. 3, or alternatively, using coextrusion supply head, the output of single extruder is separated into
Multilayer, produce multilayer film.In either event, multilayer is completely cast on casting roller, forms single laminated film.Each layer
It can be formed by identical or different material.Such as some films can be formed with three layers：The quilt constructed for contact substrate and peel ply
The sandwich layer that adhesive layer surrounds.In brief, the protective layer polymer film of extrusion can have any quantity of change or similar material
Layer.
The PE films produced using the above method will meet the requirement of many applications, but surface caused by microgel be present and do not advise
Then degree can be allowed to exclude many surface protection film applications.Despite the presence of the gel for many types that can cause this degree of irregularity
(referring to Spalding et al., " Troubleshooting and Mitigating Gels in Polyolefin Film
Products, " Plastics Engineering September 2013, pp.50-58. (" Spalding Paper ")), but
The present processes relate generally to control (1) to keep the non-dispersed polymeres chain of entanglement not melted during expressing technique, or
Person before being projected from extruder die head those (" non-molten gel " or " not melting microgel ") for solidifying, or (2) because
Oxidation or shear-induced cause those (" cross-linked gel " or " crosslinking microgels ") of crosslinking.
This two gellike (and other) may be present in the base resin of resin manufacturers' offer.Basis described above is squeezed
Go out technique and be usually removed larger gel, but removing less non-molten gel, be poorly efficient in terms of not melting microgel especially.
It is recommended that it can be removed from PE membrane materials by using relatively high (100-200kPa) shear stress level and do not melt microgel.Ginseng
See Spalding paper.Although Spalding suggests the conventional single screw rod with Maddock- type blenders can be used to squeeze
Go out machine, realize this shear stress level, but inventor has found, and it is 60-70kPa that this extruder, which is normally limited to scope,
The maximum shear stress, this proof be not enough to reduce worry microgel defect.
The not only obtainable the maximum shear stress deficiency in single screw extruder, and inventor has found, even
The relatively high shear stress level that Spalding suggests also is not enough to reduce microgel acceptable to not causing in final PE films
Rat size.Exist only by can just make not melt microgel using high shear stress in double screw extruder
It is broken in sufficient degree.However, in the absence of in the case of other measures, high temperature is found, shearing force technique causes quantity big
Cross-linked gel.
The present invention overcomes problem described above.In an illustrative embodiments, the present invention provides refined
And/or the method for being homogenized the fluoropolymer resin combined individually or with other film product compositions.In the special of this embodiment
In variant, in the method for extruding the polymer film with the microgel for being only only below required size or quantitative criteria, resin spirit
System and/or homogenizing process are used as pre-treatment step.In another illustrative embodiments, the present invention is provided containing refined and/or equal
Change the continuous film manufacturing process of base resin action.
The method of the present invention can be used for the production substantially polyolefin without microgel of the full-size more than 100 microns
Film.In special embodiment, method of the invention can be used for the full-size for producing the microgel that any of which is observed
Scope is 10 microns to 60 microns of polyolefin film.In some especially sufficient embodiments, method of the invention can be used for
The polyolefin film that the full-size scope for the microgel that production any of which is observed is 20 microns to 50 microns.The side of the present invention
Method, which can also be used for producing microgel, to be counted (the microgel quantity in 10 microns of size) and is less than 0.1/mm2Polyolefin film.Enter
One step, they can be used for producing following polyolefin films, and the polyolefin film, which is not shown from the nominal flat surfaces of film, to be prolonged
Extend over 1.0 microns of projection.
With reference to figure 4, the generalized method M100 of the refined resin of production according to an embodiment of the invention starts from S105.
At S110, resin material is provided and/or received at resin manufacturers.Any thermoplastic resin material, practice side can be used
Method M100, but as described above, it is directed primarily to the resin material with non-molten gel and microgel.Typically with can with other into
Premix or the pellet form of compounding is divided to provide resin material.At S120, other compositions material is selected.These materials may include especially
Its stabilizing material, the stabilizing material is specifically selected, to offset observed by being run into during very shearing force is extruded
Cross-linking effect.
As described above, it has been found that, the expressing technique of very shearing force (being more than 250kPa) tends to lead to extruding
High crosslinking degree in resin.The gained that this crosslinking is attributable to shearing force level itself and run into extruder is high
Both temperature.Think that shearing force environment produces the free radical of the high quantity obtained by cross-linked polymer chain in melt.High fever,
Long residence time and oxygen be present and can increase oxidation and the tendency that is further crosslinked.
In order to offset these effects, one or more stabilizing materials can be added into resin.Selected specific stabilizer
(for example, antioxidant stabilizers) can depend on main polymer, specific resin formula, used shearing without limitation
Stress level, Temperature Control Measures and other factors.
The effect of antioxidant stabilizers is that protection polymer avoids oxidation from dropping in thermoplastic polymer, such as polyethylene
Solution.The mechanism of this degraded is the free radical chain technique of self-catalysis.During this technique, hydroperoxides, hydrogen peroxide are formed
Compound resolves into free radical, and accelerated degradation.Free radical is removed by (1), interrupts and is aoxidized caused by being decomposed by hydroperoxides
Chain reaction and (2) consumption hydroperoxides, antioxidant prevent this degraded.
In example illustrated embodiments, this method can be used to refine PE and other vistanexes, extra composition can wrap
Include for offset primary antioxidant that the crosslinking relevant with heat construct or select and constructed for the free radical of consumption shear-induced or
The auxiliary antioxidant of selection.Antioxidant contains one or more hydrogen atoms, and the hydrogen atoms fetter free radical,
Especially peroxy radical, form the hydroperoxide groups of polymerization and metastable antioxidant species.Phenolic antioxidant is to work as
The antioxidant of maximum is sold in modern plastics industry.They include simple phenols, bisphenols, thiobis phenols and Polyphenols.By
Hinder phenol, such as BASFs1076,1010 and Ethyl 330 meets radicals scavenging requirement and is considered as main anti-
Oxygen agent.Other primary antioxidants include those listed in tablei.
Can be used as one group of main antioxidant of auxiliary antioxidant includes phosphorus-base antioxidant (usually phosphite ester).It is sub-
Phosphate increases alcohol to work by converting hydroperoxide into non-chain, and phosphite ester is oxidized to phosphate in itself.
Trisnonyl phenyl phosphite is a kind of wide in range phosphite ester used.Typical specific auxiliary antioxidant is GE Weston
TNPP, the BASF Hes of Ultranox 626168.Other schematical auxiliary antioxidants in table ii.
There can be non-required effect available for some or all of antioxidant for offsetting cross-linking effect, if be excessively used
Words.This effect may include such as migration and frosting.Therefore, typically it is expected that selection is offset needed for crosslinking in extrusion resin
Minimum.For specific resin or extrudate it is final using application for, empirical data optimization can be used to advocate peace auxiliary antioxygen
The relative quantity of agent.
Fig. 4 is returned to, at S130, mixed stability material and any other composition and base resin material.This can be independent
Mixing or compounding operation in realize, or can by be compounded in shearing force/hopper of extrusion device in combine each material
To realize.At S140, molten polymer mixture or sizing material, and in the shear stress down cut more than 250kPa.In typical case
Embodiment in, shear stress scope is 250kPa to 400kPa.This is typically extruded using the multiscrew of shearing force
Machine is realized, but any device that can assign this shear stress can be used.Polymer can be based on and acceptable microgel contains
The standard of amount, select the specific shear stress used in method M100.As an example, for required maximum micro- solidifying
Glue size is about 50 microns and intermediate value microgel size is less than for 20 microns of PE resin materials, it is desirable to more than cutting for 300kPa
Shearing stress.Usually, polyolefine material can claimed range be 300kPa to 375kPa shear stress.
In order to further simplify the present invention, double screw extruder, such as extruder 200 illustrated in Fig. 5 can be used, enter
Row method M100 action S140.Extruder 200, which includes polymer resin mixture 10, can be incorporated into extruder barrel 210
Hopper 211.In some embodiments, hopper 211 and extruder barrel 210 may include that nitrogen can replace oxygen through its introducing
Port 214, and then aid in reduce melt in oxidation.Inside the extruder using nitrogen covering can aid in reducing in melt with
The relevant crosslinking of heat.Then by twin-screw 212, make to be guided through machine barrel 210 after resin 10, this assigns required height
Shear stress level.Then melt polymer material is made to pass through die head exit 218, it is with refined polymer extrudate herein
10' forms are extruded.In the embodiment illustrated, refined polymeric material 10' is extruded in the form of club, but can be used
Any suitable cutter device 219 cuts into pellet.Then can pack these pellets and shift for be processed further and/or
It is used as basic material in standard extruding production line.As described below, extruder 200 can or in Continuous maching line use for life
Produce final application material.
Fig. 4 is turned again to, method M100 may include the action for drawing VOC (VOCs), and it can be used as
Result that melt internal stabilizer reacts and is exposed under high stress level and occur.Extruder 200 is enumerated in Fig. 5, and this can
Realized by using one or more ports 216 near vacuum pipeline to the end of extruder barrel 210.At S160, squeeze
Go out refined polymeric material.In some embodiments, extrudate can have solidification polymer bar form, it is cleavable into
Pellet, its size are substantially similar to the base resin pellet of resin manufacturers' offer.This method is terminated at S195.
The extruded polymer obtained by above-mentioned technique is the refined forms of starting base polymer.If apply sufficient shearing
Stress, then the technique will remove all big gels not melted and the size for significantly reducing any residual microgel and without notable
Produce cross-linked gel.
Method M100 refined polymer output can be only base polymeric material, reduce cross-linked gel institute
Any stabilizer used, and from any reactant therein.Then in the expressing technique of routine, can be used this refined
The material substitution base resin crossed.In this case, can in the extruder of routine or a part as pre-mixing process,
Before being incorporated into conventional extruders, refined resin material and any other final material composition are mixed or are compounded.
Or any this final material composition and base resin can be mixed or are compounded as acting S120 in above method M100
A part.
It is used as producing with Fig. 3 extruded film using the refined resin granular material of shearing force process for refining M100 productions
The input material of the similar film production line of line 100.With reference to figure 6, the method M200 for forming polymer film in such a way is started from
S205.At S210, polymer and any other composition for final membrane material are selected.Composite material can especially include above
The stabilizing material offset selected by cross-linking effect of description.At S220, various component of polymer are blended together.It is appreciated that
Before shearing force compounding, some or all of compositions can be blended.However, in some cases, squeezed in the shear stress of routine
Go out during or before action, some final material compositions and the refined polymer of shearing force compounding action can be blended
Output.At S230, using previously described very high shear stress, compounding base polymer resin and at least it is any surely
Determine additive.Gained compounding/refined resin material then can be formed as pellet at S240 or other can transporting pattern.
In some embodiments of the present invention, it can realize that shearing force is matched somebody with somebody as a part for single Continuous maching line
Mixed action.In this case, because shearing force compounding action can be as the input thing of conventional magnetic shear stress compounding action
Directly provide, therefore action S240 can be saved.At S250, compounding/refined polymer resin material is fed to routine
Shear stress extruder in.Before or during extruder feed process, compounding/refined resin material and its can be mixed
His final product component.Extra composition may include the refined other polymers resin of the method according to the invention and/or
There is no refined fluoropolymer resin.In an extruder, final material composition, which completely melts, is placed in conventional shear stress
Under power.At S260, the polymeric material of melting may pass through one or more filters, the filter preferably as close possible to
Arranged in extrusion die, to avoid reassociating in filter downstream microgel.At S270, extruded polymer material is simultaneously being cast
It is cast on roller.In various embodiments, polymeric material can be used as single tunic to be cast or can be used as previously described
A laminar flow in multilayer film prolongs.It can be formed with including living through the additional layer of shearing force process for refining and/or not including
One or more layers this multilayer film of any this resin.
Method M200 is terminated at S295.
It is cast or extrudes it is appreciated that is not limited to specific film using the refined resin of the present invention and resin purification method
Technique.They for example can be used with any curtain coating or blow molding die process integration.It is also to be understood that except extrusion/coextrusion processes with
Outside, a part that can also be before other techniques or as other techniques, it is (such as square using the resin purification method of the present invention
Method M100).
Compared with by the film of unpurified production of resins, the film product produced using the inventive method has what is drastically declined
Microgel content and the definition improved.Especially can be used the present invention method, there is provided refined polyolefin material and
The film formed by it.Most particularly, this method can be used to be formed has not achievable microgel size and number level in the past
Refined PE resin materials and PE films.According to embodiment of the present invention, it is possible to provide substantially big without full-size
In the PE resin materials and PE films of 100 microns of gels.In some variants, it is possible to provide the full-size scope of maximum microgel
The PE resin materials and PE films for being about 10 microns to about 60 microns.In special embodiment, it is possible to provide full-size scope
It is about 10 microns to about 40 microns of PE resin materials.According to embodiment of the present invention, microgel quantitative range can be also provided
For 0-0.2/mm2The PE resin materials and PE films of microgel of the full-size more than 10 microns.In some embodiments, PE trees
It is 0 to 0.1/mm that fat material and PE films, which can have scope,2Full-size scope is about 10 microns to about 50 microns of microgel
Average microgel counts.
By limiting the size of the microgel included in film product, it is minimum raised that method of the invention also allows production to have
Film.Especially, according to embodiment of the present invention, it is possible to provide the maximum height of projection scope of film on nominal flat surfaces
It is about 0.0 to about 5.0 micron of PE membrane materials.In particularly preferred embodiments, PE films do not have substantially and nominally put down
1.0 microns of projection is highly greater than about on smooth surface.
The thickness range of the PE films produced according to an embodiment of the present invention is typically about 15 microns to about 80 microns.One
In a little required embodiments, the thickness range of PE films can be about 20 microns to about 60 microns.In particularly preferred embodiment party
In case, the thickness range of PE films is about 25 microns to about 40 microns.Any previously described stabilizer can be used, form PE membrane materials
Material, and it can also include polypropylene (PP) without limitation, ethylene vinyl acetate (EVA), ethylene methyl acrylate (EMA),
Ethylene methacrylic acid (EMMA), ethylene n-butyl acrylate (EnBA), plastic body, for example, the butylene of metallocene catalysis, amylene,
The copolymer of hexene or octene and ethene, elastomer or block copolymer, such as s-B-S (SBS), benzene
Ethylene-vinyl-butylene-styrene (SEBS) and styrene-isoprene-phenylethene (SIS), catalyst neutralization agent, such as firmly
Resin acid calcium and other, use the LLDPE of other Catalyst Productions, and tackifier.PE films produced by the invention are formed as
Simple layer or the multilayer with identical or different composite material.In some multilayer embodiments, whole group quantity is only only below
The layer of (subset number) according to the refined PE resins of the inventive method by forming.
Examined effect
For surface protection film, an effect of harsh microgel inclusion and surface topography requirement is standard
Examined effect may not be sufficient.Unacceptable raised microgel size can be caused so small at film surface, so that
They can not possibly be detected by conventional method.In order to evaluate the refined resin material for using the inventive method to produce and surface
The purpose of diaphragm, it is desirable to new Examined effect.Following paragraphs, which describe the data that offer describes in the examples below, to be made
Detection method.
Usually, by both artificial and automatic modes can count and microgel size detection.Used side
Method may depend on the quality and uniformity on film surface.If there is film flat consistent adhesive surface (that is, to contact substrate to be protected
Surface), then preferable automatic mode.If however, film have change or coarse surface, preferable manual method, with
Reduce noise data.
In manual method, the count requirement of microgel uses the stereoscope of 20 times of amplification effects, in coaxial reflection
Under illumination, naked eyes detect sample pane.Just as illustrated in fig. 7, checked in the sample pane 300 of membrane material predetermined quantity with
Put 310 in seat in the plane.At each position 310, amplify rectangular area, it is allowed to identify and count the microgel in the opening position.Institute
In the example of elaboration, the region of amplification is 4.68x3.52mm (16.4736mm2).Then it is recordable in micro- solidifying at each position
The quantity of glue 320, and counted for providing the estimation in unit area.
Imaging software, such as Media Cybernetics can be usedRealize the hand size of microgel
Measurement.Such asWith determining the microgel that above identifies in the capture images shown in the sectional drawing in Fig. 8
" measurement " function workable for full-size.Then these measurement results can be used, determine micro- solidifying in the range of various sizes
Glue frequency.
For the counting and dimensional measurement of automation, the stereoscope sum code-phase of 20 times of amplification effects is used
Machine, under coaxial indirect illumination, the capture images from sample pane.It can be captured in the random position of the predetermined quantity on each frame
The image of amplification.Then special image analysis software is used, there is provided counting and dimension information.
Surface topography and especially height of projection are high-importance for surface protection film.For following embodiment
For, using withThe Zygo NewView7300Scanning White Light of software
Interferometer, determine the height of projection in nominal surface plane.Special application is developed, is measured in average surface
Height of projection on plane.This technology allows the height of projection of as low as 0.1 micron of measure.
In addition to microgel and measuring surface form, the mist degree of membrane sample is also examined.Term mist used herein
Degree (also referred to as wide angle scattering) refers to the percentage for deviateing the transmitted light that penetrates membrane sample of the incident beam more than 2.5 °.For with
For lower embodiment, according to ASTM D1003-95, haze measurement is realized.Sampling, sample preparation, equipment, test parameter and calculating are all
Carried out in the range of ASTM D1003-95a.
Embodiment
Embodiment 1
As baseline, using the similar conventional magnetic shear stress extrusion line described with Fig. 3, multilayer PE films are formed.Multilayer bag
Include sandwich layer, adhesive layer and peel ply.Sandwich layer is by 99.992% low density polyethylene (LDPE) (LDPE) and the shapes of 0.008%Irganox 1010
Into.Adhesive layer is formed by 75% butylene copolymer polyethylene plastomers, 15% high density polyethylene (HDPE) (HDPE) and 10%LDPE.Stripping
Absciss layer is formed by 85%LDPE and 15%HDPE.Each layer of composition is premixed, and three kinds of mixtures are independently fed to three
In individual single screw extruder.In each extruder, polymeric material is placed in about 66kPa estimation the maximum shear stress
Descend and pass through multiple fillter sections including final 5 microns of fondant filters.The melt extrusion of filtering by film die head, and
Single trilamellar membrane is cast on smooth casting roller.Then the film of cooling is collected on winder.Take out membrane sample and use
Technical checking described above, to determine microgel size and count information.
Embodiment 2
Using the shearing force method similar with M200, refined multilayer PE films are formed.Multilayer film includes sandwich layer, glues
Close layer and peel ply.Sandwich layer and peel ply are by 59.4%LDPE, 40%HDPE, 0.48%1076 Hes
0.12%168 form.Adhesive layer is by 75% butylene copolymer polyethylene plastomers, 15%HDPE, and 9.56%
LDPE, 0.32%1076 and 0.12%168 form.
Merga pass high shear extruder is independently mixed for the composition of adhesive layer and for the composition of sandwich layer and peel ply
Processing.In either case, by the double screw extruder of the rotating Vortex of material feeding to shearing force, they are passed through herein
Go through about 350kPa estimation the maximum shear stress.By the way that nitrogen is injected into the hopper and machine barrel of extruder, there is provided nitrogen covers
Lid.Vacuum ports close to extruder barrel end are used to draw VOCs.Resulting polymers are extruded through die head and cut into
Pellet.Collect pellet and pack and seal for transport.The pellet then packed is sealed off, and is fed to three single screw rods and is squeezed
Go out in machine, adhesion-layer materials are fed in an extruder and by sandwich layer/peel ply material feeding to two extruders.
In each extruder, polymeric material undergoes about 50kPa estimation the maximum shear stress, and through including final 5 microns of melts
Multiple fillter sections including filter.By the melt extrusion of filtering by film die head, and list is cast on smooth casting roller
Only trilamellar membrane.Then the film of cooling is collected on winder.Take out membrane sample and use technical checking described above, to survey
Determine microgel size and count information.
Embodiment 3
Using the shearing force method similar with M200, another refined multilayer PE films are formed.This multilayer film bag
Include sandwich layer, adhesive layer and peel ply.Sandwich layer and peel ply are by 59.85%LDPE, 40%HDPE, 0.06%
1076 and 0.09%Sandostab P-EPQ are formed.Adhesive layer is by 54.85% butylene copolymer polyethylene plastomers, and 30%
HDPE, 15% ethylene octene elastomer, 0.09%1076 and 0.09%Sandostab P-EPQ are formed.
As in Example 2, be independently mixed for the composition of adhesive layer and for the composition of sandwich layer and peel ply simultaneously
Through high shear extruder.In either case, material experience about 350kPa estimation the maximum shear stress, extrudes and cuts into
Pellet.As before, pellet is fed in three extruders and is coextruded, form trilamellar membrane piece.In each extruder,
Polymeric material undergoes about 50kPa estimation the maximum shear stress.Before extrusion, material passes through multiple fillter sections, the mistake
Filter section includes final 7.5 microns of fondant filter in this case.Take out the sample of gained film and using described above
Check-up, determine microgel size and projection information.
Table III is outlined for three samples for each, the content of microgel and raised altitude information.Each
In the case of, data are obtained from least ten membrane sample, wherein examining each membrane sample as described above.It can be seen that, with conventional shape
Into PE materials compare, using the present invention shearing force process for purification formed two kinds of PE membrane materials show significantly it is smaller
Microgel.Further, refined PE resins membrane material does not show the projection more than 1.0 microns, and embodiment 3
Film is shown without the projection more than 0.2 micron.
Table III
* full-size>10 μm of microgel
In addition to microgel size and number decline, refined PE membrane materials also show that unexpected mist degree is big
The result that width declines.The improvement of the definition of membrane material is more than only as desired by the measurable decline of the naked eyes of microgel.This
Show in membrane material the very uniformity of high level.
It should be readily apparent to one skilled in the art that the present invention is sensitive to wide purposes and application.Without departing from the present invention's
In the case of spirit or scope, reasonably suggested according to the present invention and its preceding description or by it, except it is described herein that
Many embodiments of the invention and reorganization beyond a little, and many changes, modified and equivalent layout is obvious.
Although above illustrate and describe the present invention enumerate embodiment, it is to be understood that the present invention be not limited to herein
Disclosed structure.In the case of without departing from its spirit or inner characteristic, the present invention can embody in other specific forms.
Claims (22)
1. a kind of method of finished polymer resin material, this method include：
Molten resin material is simultaneously placed under the shear stress that scope is 250kPa to 400kPa, forms refined resinous wood
Material.
2. the method for claim 1 wherein polymer resin material is mainly made up of one or more polyolefin.
3. the method for claim 1 wherein polymer resin material is mainly made up of polyethylene.
4. the method for claim 1, further comprises：
Mixed polymer resin material and one or more antioxidant.
5. the method for claim 1 wherein polymer resin material is placed in into the shear stress that scope is 300kPa to 375kPa
Under, form refined resin material.
6. the method for claim 1, further comprises：
Extrude the resin material that simultaneously solidifying refinement is crossed.
7. the method for claim 1 wherein polymer resin material is further including at least the polyethylene of main by weight, this method
Including：
Mixed polymer resin material and one or more antioxidant；With
Extrude the resin material that simultaneously solidifying refinement is crossed.
8. a kind of method for forming polymer film, this method include：
The polymer resin material being mainly made up of polyethylene is provided；
The polymer resin material and one or more antioxidant are mixed, forms resin material mixture；
Melt the resin material mixture and be placed under the shear stress that scope is 250kPa to 400kPa, formation refined
Resin material；With
The refined resin material is extruded, forms polymer film.
9. the method for claim 8, further comprises：
Before refined resin material is extruded into the action of polymer film, the resinous wood that simultaneously solidifying refinement is crossed is extruded
Material；With
The extrusion and the refined resin material solidified are melted, and is placed under the shear stress less than 70kPa.
10. a kind of resin material being substantially made up of polyethylene, the resin material is substantially more than 100 without full-size
The microgel of micron.
11. the resin material of claim 10, wherein by melting precursor resin material, and scope is placed on as 250kPa extremely
Under 400kPa shear stress, the resin material is refined.
12. the resin material of claim 10, wherein by melting precursor resin material, and scope is placed on as 300kPa extremely
Under 375kPa shear stress, the resin material is refined.
13. the resin material of claim 10, the wherein resin material are extrusion pellet form.
14. a kind of thermoplastic polymer film being substantially made up of polyethylene, the film is substantially more than 100 without full-size
The microgel of micron.
15. the thermoplastic polymer film of claim 14, the wherein film are substantially micro- more than 50 microns without full-size
Gel.
16. the thermoplastic polymer film of claim 14, the wherein film have at least one nominal flat surfaces, the surface
Substantially without the projection that 1.0 microns are extended outwardly beyond from the nominal flat surfaces.
17. the thermoplastic polymer film of claim 14, the wherein film have at least one nominal flat surfaces, the surface
Substantially without the projection that 0.5 micron is extended outwardly beyond from the nominal flat surfaces.
18. a kind of multi-layer thermoplastic polymer film, it includes：
Define the peel ply of the first exterior film surface；With
The adhesive layer that defines second exterior film surface relative with the first exterior film surface,
At least one wherein in peel ply and adhesive layer is substantially made up of and substantially big without full-size polyethylene
In 100 microns of microgel.
19. the multi-layer thermoplastic polymer film of claim 18, wherein both peel ply and adhesive layer are substantially by polyethylene group
Into and be substantially more than 100 microns of microgel without full-size.
20. the multi-layer thermoplastic polymer film of claim 18, the wherein film do not have substantially from the first or second outer membrane
Surface extends outwardly beyond 1.0 microns of projection.
21. the multi-layer thermoplastic polymer film of claim 18, the wherein film do not have substantially from the first or second outer membrane
Surface extends outwardly beyond 0.5 micron of projection.
22. the multi-layer thermoplastic polymer film of claim 18, wherein adhesive layer include the butene of 55% to 75% weight
The high density polyethylene (HDPE) of thing polyethylene and 15% to 30% weight.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201562171473P | 2015-06-05 | 2015-06-05 | |
| US62/171,473 | 2015-06-05 | ||
| PCT/US2016/035770 WO2016196965A1 (en) | 2015-06-05 | 2016-06-03 | Low microgel surface protection film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107848048A true CN107848048A (en) | 2018-03-27 |
| CN107848048B CN107848048B (en) | 2020-11-13 |
Family
ID=57442211
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680040884.0A Expired - Fee Related CN107848048B (en) | 2015-06-05 | 2016-06-03 | Low microgel surface protective film |
Country Status (9)
| Country | Link |
|---|---|
| US (2) | US20160355650A1 (en) |
| EP (1) | EP3302859A4 (en) |
| JP (1) | JP6814749B2 (en) |
| KR (1) | KR20180014155A (en) |
| CN (1) | CN107848048B (en) |
| BR (1) | BR112017026115A8 (en) |
| IL (1) | IL256023A (en) |
| TW (1) | TWI611894B (en) |
| WO (1) | WO2016196965A1 (en) |
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| CA2229273A1 (en) * | 1998-02-10 | 1999-08-10 | Balke, Steven T. | Polymer segregation process |
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2016
- 2016-06-03 BR BR112017026115A patent/BR112017026115A8/en not_active IP Right Cessation
- 2016-06-03 CN CN201680040884.0A patent/CN107848048B/en not_active Expired - Fee Related
- 2016-06-03 TW TW105117644A patent/TWI611894B/en not_active IP Right Cessation
- 2016-06-03 EP EP16804543.3A patent/EP3302859A4/en not_active Withdrawn
- 2016-06-03 KR KR1020187000012A patent/KR20180014155A/en unknown
- 2016-06-03 US US15/172,660 patent/US20160355650A1/en not_active Abandoned
- 2016-06-03 WO PCT/US2016/035770 patent/WO2016196965A1/en active Application Filing
- 2016-06-03 JP JP2017562622A patent/JP6814749B2/en active Active
-
2017
- 2017-11-30 IL IL256023A patent/IL256023A/en unknown
-
2019
- 2019-08-20 US US16/545,780 patent/US20200002489A1/en not_active Abandoned
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20180014155A (en) | 2018-02-07 |
| WO2016196965A1 (en) | 2016-12-08 |
| US20200002489A1 (en) | 2020-01-02 |
| EP3302859A1 (en) | 2018-04-11 |
| EP3302859A4 (en) | 2019-02-13 |
| BR112017026115A2 (en) | 2018-08-14 |
| TWI611894B (en) | 2018-01-21 |
| CN107848048B (en) | 2020-11-13 |
| TW201716201A (en) | 2017-05-16 |
| JP6814749B2 (en) | 2021-01-20 |
| IL256023A (en) | 2018-01-31 |
| BR112017026115A8 (en) | 2022-12-27 |
| US20160355650A1 (en) | 2016-12-08 |
| JP2018519376A (en) | 2018-07-19 |
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